JP3033327B2 - Thermosetting resin composition and copper-clad laminate using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a thermosetting resin composition and a copper-clad laminate using the same.
More specifically, the present invention relates to a thermosetting resin composition having a low dielectric constant and excellent heat resistance, and a copper-clad laminate using the same.

[0002]

2. Description of the Related Art Thermosetting resins are widely used as matrix resins for printed wiring boards. In recent years, high-speed response of circuits on printed circuit boards accompanying high-speed operation of semiconductor elements in high multilayer printed wiring boards for high-speed computers. Sex is being demanded. The signal propagation speed on a printed circuit board depends on the dielectric constant of an insulating material holding the circuit, and a material having a lower dielectric constant has a higher propagation speed. For such applications, polyimide resins and heat-resistant epoxy resins have been used so far.

[0003]

However, conventional polyimide resins and heat-resistant epoxy resins have excellent heat resistance, but the dielectric constant of the resin alone is as high as 3.4 to 3.9.
-The dielectric constant of the laminate in combination with the glass cloth is even higher, between 4.5 and 5.0. A method of modifying the laminate with polybutadiene or the like to reduce the dielectric constant of the laminate to 4.0 or less has also been proposed, but has a drawback of lowering heat resistance and has not been put to practical use. Therefore, a resin composition having a dielectric constant of 4.0 or less without losing heat resistance has been desired.

[0004]

Means for Solving the Problems As a result of diligent studies conducted by the present inventors to solve the above-mentioned problems, the present inventors have found that a resin composition containing a specific polymaleimide compound as an essential component fulfills the above-mentioned objects. Was completed.

That is, the present invention provides a compound represented by the general formula (1):

Embedded image (Wherein P is independently an alkyl group having 1 to 10 carbon atoms, an alkyloxy group or an alkylthio group, an aryl group having 6 to 10 carbon atoms, an aryloxy group or an arylthio group, a cycloalkyl group having 5 to 10 carbon atoms) , Represents a halogen atom, a nitro group, a hydroxyl group or a mercapto group,
j represents an integer value of 0 or more and 4 or less. When j is 2 or more and 4 or less, P may be the same or different in the same ring. Q independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group or an alkylthio group, an aryl group having 6 to 10 carbon atoms, an aryloxy group or an arylthio group, a halogen atom, a hydroxyl group or a mercapto group; Indicates an integer value of 3 or less. k is 2 or more and 3
In the following cases, Q may be the same or different in the same ring. X is a general formula (2):

[0006]

Embedded image (Wherein, Q and k are the same as those described above, n is the average number of repeating units, and is a numerical value of 0.5 or more and 20 or less). A) a thermosetting resin composition comprising a polymaleimide compound (A) represented by the formula (I) and a reaction component (B) which reacts with the maleimide compound to form three-dimensional crosslinking; The present invention relates to a copper-clad laminate obtained by laminating a prepreg obtained by dissolving a base material in a molten state, drying the prepreg and a copper foil, and laminating and heating.

Next, a method for producing the polymaleimide compound used in the present invention will be described. General formula (3):

[0008]

Embedded image (However, each Y is independently

[0009]

Embedded image A monovalent functional group selected from the group consisting of
The ortho position of at least one of the two Ys is a hydrogen atom,
Q and k are the same as described above. And a compound represented by the general formula (4):

[0010]

Embedded image (However, at least one of the ortho and para positions of the amino group is a hydrogen atom, and P and j are the same as those described above). By reacting in the presence, an intermediate polyamino oligomer represented by the general formula (5) is obtained.

[0011]

Embedded image (In the formula, P, Q, j, k and X represent the same as described above.)

In the polyamino oligomer represented by the general formula (5), X represents the structure of the general formula (2),
In the aniline or a derivative thereof represented by the general formula (4), when j is 3 or less and at least two of the ortho and para positions of the amino group are hydrogen atoms, the general formula (6) Represented structure

[0013]

Embedded image (However, P, Q, j and k are the same as described above. M is the number of repeating units and represents an integer of 1 or more and 20 or less.).

In the structure of the general formula (2), which is a feature of the polymaleimide compound used in the present invention, the average number of repeating units n is low at the melting point (low softening point), low in melt viscosity and excellent in operability. Therefore, the average value is 0.5 or more and 20 or less, preferably 0.5 or more and 10 or less. If n is less than 0.5, the content of the high-melting substance is too large, which is inconvenient. If n exceeds 20, the functional group density decreases and heat resistance deteriorates.

The compound represented by formula (3) (compound (A)) used in the present invention is not particularly limited, but is typically p- or m-diisopropenylbenzene, p- And m-bis (α-hydroxyisopropyl) benzene, 1- (α-hydroxyisopropyl)
-3-Isopropenylbenzene or a mixture thereof is used. Also, a substituted alkyl group of these compounds,
For example, diisopropenyltoluene and bis (α-hydroxyisopropyl) toluene can also be used,
Further, it is also possible to use a halogen-substituted product such as chlorodiisopropenylbenzene and chlorobis (α-hydroxyisopropyl) benzene.

In addition, specifically, the following compounds can be exemplified. 2-chloro-1,4-diisopropenylbenzene, 2-chloro-1,4-bis (α-hydroxyisopropyl) benzene, 2-bromo-1,4-
Diisopropenylbenzene, 2-bromo-1,4-bis (α-hydroxyisopropyl) benzene, 2-bromo-1,3-diisopropenylbenzene, 2-bromo-
1,3-bis (α-hydroxyisopropyl) benzene, 4-bromo-1,3-diisopropylbenzene,
-Bromo-1,3-bis (α-hydroxyisopropyl) benzene, 5-bromo-1,3-diisopropenylbenzene, 5-bromo-1,3-bis (α-hydroxyisopropyl) benzene, 2-methoxy- 1,4-diisopropenylbenzene, 2-methoxy-1,4-bis (α-hydroxyisopropyl) benzene, 5-ethoxy-1,3-diisopropenylbenzene, 5-ethoxy-1,3-bis (α -Hydroxyisopropyl) benzene, 2-phenoxy-1,4-diisopropenylbenzene, 2-phenoxy-1,4-bis (α-hydroxyisopropyl) benzene, 2,4-diisopropenylthiol, 2,4-bis (Α-hydroxyisopropyl) thiol, 2,5-diisopropenylthiol, 2,5-
Bis (α-hydroxyisopropyl) thiol, 2-methylthio-1,4-diisopropenylbenzene, 2-methylthio-1,4-bis (α-hydroxyisopropyl)
Benzene, 2-phenylthio-1,3-diisopropenylbenzene, 2-phenylthio-1,3-bis (α-hydroxyisopropyl) benzene, 2-phenyl-1,
4-diisopropenylbenzene, 2-phenyl-1,4
-Bis (α-hydroxyisopropyl) benzene, 5-
Naphthyl-1,3-diisopropenylbenzene, 5-naphthyl-1,3-bis (α-hydroxyisopropyl)
Benzene, 2-methyl-1,4-diisopropenylbenzene, 2-methyl-1,4-bis (α-hydroxyisopropyl) benzene, 5-butyl-1,3-diisopropenylbenzene, 5-butyl-1 , 3-Bis (α-hydroxyisopropyl) benzene.

The compound represented by the above general formula (4) (hereinafter referred to as compound (B)) is typically aniline, for example, chloroaniline, dichloroaniline, toluidine, xylidine, phenylaniline, nitroaniline. Aniline, aminophenol, cyclohexylaniline and the like can be used. In addition, methoxyaniline,
Examples thereof include ethoxyaniline, phenoxyaniline, naphthoxyaniline, aminothiol, methylthioaniline, ethylthioaniline and phenylthioaniline.

In the method for producing the polyamino oligomer represented by the general formula (5) used in the present invention, the compound (A) and the compound (B) are used in a molar ratio of the compound (B) to the compound (A) (the compound (A)). (B) / Compound (A)) is initially charged at 0.1 to 2.0, preferably 0.2 to 1.0, and reacted, and then compound (B) is added to the previously added compound ( 0.5 to 20 in a molar ratio to A) (as described above).
By adding an additional amount of 0, preferably 1.0 to 5.0, a polymaleimide compound having a characteristic structure can be obtained. In addition, this two-stage reaction gives a favorable result in terms of completion of the reaction or operability.

The acid catalyst used in the above reaction includes inorganic acids such as hydrochloric acid and sulfuric acid, organic acids such as benzenesulfonic acid and toluenesulfonic acid, activated clay, acidic clay, silica alumina,
Zeolites, solid acids such as strongly acidic ion exchange resins, heteropolyhydrochloric acid and the like can be mentioned, but a solid acid that can easily remove the catalyst by filtration after the reaction is preferable in operation,
When another acid is used, neutralization with a base and washing with water are performed after the reaction.

The acid catalyst is used in an amount of 5 to 40% by weight based on the total amount of the compounds (A) and (B) as raw materials to be initially charged. 10 from the point
３０30% by weight gives favorable results. The reaction temperature is usually selected in the range of 100 to 300 ° C. However, in order to suppress the generation of the isomer structure and to avoid side reactions such as thermal decomposition, the reaction temperature is set at 16 ° C.
0-230 ° C is preferred.

The reaction time is usually shorter than the above range under the above-mentioned temperature conditions, since the reaction does not proceed completely when the reaction time is short, and a side reaction such as thermal decomposition of the product occurs when the reaction time is long. It is selected in the range of 2 to 48 hours, but preferably in the range of 6 to 24 hours in total.

In the method for producing the polyamino oligomer, since aniline or a derivative thereof also serves as a solvent, another solvent is not necessarily used, but a solvent can be used. For example, in the case of a reaction system that also serves as a dehydration reaction,
Specifically, when reacting a compound having an α-hydroxypropyl group as a raw material, after the dehydration reaction is completed using an azeotropic dehydration solvent such as toluene or chlorobenzene, the solvent is distilled off, The reaction may be carried out in the above-mentioned temperature range.

The polymaleimide compound used in the present invention is prepared by charging a polyamino oligomer represented by the general formula (5) obtained by the above-mentioned method into a reactor, dissolving the polyamino oligomer in a suitable solvent, and dissolving with maleic anhydride. It is obtained by reacting in the presence of an agent, a catalyst and a base, removing unreacted maleic anhydride and other impurities by washing with water or the like after the reaction, and removing the solvent under reduced pressure.

The polymaleimide compound used in the present invention has a skeleton represented by the general formula (1) as described above. X has a structure represented by the general formula (2), and when j is 3 or less and at least two of the ortho and para positions of the amino group are hydrogen atoms, a structure corresponding to the general formula (6); That is, the structure represented by the general formula (7) is also included as the structure of X.

[0025]

Embedded image (In the formula, P, Q, j, k and m represent the same as described above.) The value of the average number of repeating units n of the structure X is a low softening point, a low melt viscosity, a high heat deformation temperature, or a high glass transition. It is preferably 0.5 or more and 10 or less from the point of view.

Examples of the organic solvent used in the above-mentioned polymerization reaction include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and acetophenone, N, N-dimethylformamide, and the like.
Aprotic solvents such as N, N-dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, acetonitrile, and sulfolane; cyclic ethers such as dioxane and tetrahydrofuran; esters such as ethyl acetate and butyl acetate; chlorobenzene; Examples thereof include halogen solvents such as chlorobenzene, chloroform, carbon tetrachloride, dichloroethane, and trichloroethane. Of these, methyl isobutyl ketone is particularly preferred.

In the polymaleimidation reaction, the above-mentioned polyamino oligomer and maleic anhydride are used in an amount equivalent to maleic anhydride to amino equivalent of polyamino oligomer in the range of 1 to 1.5, preferably 1.1 to 1.2. And the reaction is preferably carried out in an organic solvent having a weight ratio of 1 to 50, preferably 2 to 5 with respect to the total amount of the polyamino oligomer and maleic anhydride.

The dehydrating agent used in the polymaleimidation reaction is as follows:
Lower aliphatic carboxylic acid anhydrides such as acetic anhydride, propionic anhydride, butyric anhydride, phosphorus pentoxide, calcium oxide,
Examples thereof include oxides such as barium oxide, inorganic acids such as sulfuric acid, and porous ceramics such as molecular sieve. Preferably, acetic anhydride can be used.

Examples of the catalyst used in the polymaleimidation reaction include inorganic salts such as acetates such as nickel, cobalt, sodium, calcium, iron, lithium and manganese, chlorides, bromides, sulfates and nitrates. Particularly, nickel acetate is preferably used. Bases that can be used in the same manner include triethylamine, tri-n-butylamine, N-methylpiperazine, N, N-dimethylbenzylamine, and 1,8-diazabicyclo [5,4,0].
Inorganic alkalis such as tertiary amines such as -7-undecene and sodium and potassium carbonates can be exemplified, but preferably triethylamine is used.

There are no particular restrictions on the amounts of the dehydrating agent, catalyst, and bases used in the polymaleimidation reaction.
The dehydrating agent is used in an amount of 1 to 3 moles, preferably 1 to 1.5 moles, and the catalyst is used in an amount of 0.0001 to 1 equivalent to 1 equivalent of the amino group of the polyamine.
1.0 mol, preferably 0.001 to 0.1 mol, and the bases are 0.01 to 1.0 mol, preferably 0.05 to 0.1 mol.
5 moles. The reaction conditions for the polymaleimidization are as follows: the polyamino oligomer and the maleic anhydride are charged at the above ratio, and the mixture is reacted at a temperature of 10 to 100 ° C., preferably 30 to 50 ° C. for 1 to 12 hours, preferably 4 to 8 hours. ,
20 to 110 ° C. by adding the above dehydrating agent, catalyst and bases,
The reaction is preferably performed at a temperature of 50 to 80 ° C for 2 to 24 hours, preferably 6 to 10 hours.

The thermosetting resin composition of the present invention comprises the polymaleimide compound (A) of the general formula (1) and the reaction component (B). As the reaction component (B), a component that produces three-dimensional crosslinking by reacting with the unsaturated bond of the polymaleimide compound is used. As such a reaction component (B),
Preferably, triallyl isocyanurate or aromatic diamine can be used.

Illustrating the aromatic diamine,
4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylether, 3,4′-diaminodiphenylether,
2,2-bis (4-aminophenoxy) propane, 2,
2-bis (4-aminophenoxy) hexafluoropropane, 4,4′-diaminodiphenylsulfone,
3,3'-diaminodiphenylsulfone, 4,4'-
Diaminobenzophenone, 3,3'-diaminobenzophenone, 3,3'-diaminobenzophenone, 2,4-
Toluenediamine, 2,6-toluenediamine, m-phenylenediamine, p-phenylenediamine, benzidine, 4,4′-diaminodiphenylsulfide, 3,
3'-dichloro-4,4'-diaminodiphenylsulfone, 3,3'-dichloro-4,4'-diaminodiphenylpropane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'- Dimethoxy-4,4 '
-Diaminobiphenyl, 3,3'-dimethyl-4,
4'-diaminobiphenyl, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 2,2-bis (4-aminophenoxyphenyl) propane, 2,2-bis (4-aminophenoxyphenyl) hexafluoropropane, 4,4′-bis (4-aminophenoxy) diphenylsulfone, 4,
4'-bis (3-aminophenoxy) diphenylsulfone, 9,9'-bis (4-aminophenyl) fluorene, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 2,4-diaminoanisole, Screw (3
-Aminophenyl) methylphosphine oxide, 4,
4'-methylene-bis-o-chloroaniline, tetrachlorodiaminodiphenylmethane, m-xylylenediamine, p-xylylenediamine, 4,4'-diaminostilbene, 5-amino-1- (4'-aminophenyl) −
1,3,3-trimethylindane, 6-amino-1-
(4'-aminophenyl) -1,3,3-trimethylindane, 5-amino-6-methyl-1- (3'-amino-4'-methylphenyl) -1,3,3-trimethylindane, 7 -Amino-6-methyl-1- (3'-amino-4'-methylphenyl) -1,3,3-trimethylindane, 6-amino-5-methyl-1- (4'-amino-3'- One or two of methylphenyl) -1,3,3-trimethylindane, 6-amino-7-methyl-1- (4′-amino-3′-methylphenyl) -1,3,3-trimethylindane, etc. There are more than seeds.

The alkenyl group-containing compounds such as bismaleimides, allyl ether compounds, allylamine compounds, triallyl cyanurate, alkenylphenol compounds, and vinyl group-containing compounds can be used in the resin composition of the present invention within a range not to impair the purpose. A polyolefin compound or the like can be added. Further, other thermosetting resins, for example, thermosetting polyimide resin, epoxy resin, phenol resin, cyanate resin and the like can be appropriately compounded according to the purpose.

In particular, a flame retardant having a reactive group can be added for the purpose of imparting flame retardancy to the laminate. It is preferable to add bromine in an amount of 5 to 20% by weight in the resin.

The quantitative ratio of each component of the resin composition of the present invention can be appropriately selected according to the desired performance. However, triallyl isocyanate is preferably blended in an amount of 5 to 50% by weight of the whole resin composition. Preferably, more preferably 1
0 to 30% by weight. In the case of an aromatic diamine, the equivalent ratio of the double bond of the polymaleimide compound and the active hydrogen of the aromatic diamine is such that the double bond equivalent / active hydrogen equivalent = 0.5 to
It is preferable to mix them so as to be 2.0, and more preferably the ratio is 0.8 to 1.5.

The thermosetting reaction of the resin composition of the present invention can be easily carried out in the absence of a catalyst. However, when a faster reaction is desired, a polymerization initiator such as an organic peroxide or an azo compound, a phosphine compound, The addition of a basic catalyst such as a tertiary amine is effective. For example, benzoyl peroxide,
Dicumyl peroxide, azobisisobutyronitrile,
Triphenylphosphine, triethylamine, imidazoles and the like, the amount of addition is 0.05 to the total of the resin composition
5% by weight is preferred.

The production of a copper-clad laminate using the thermosetting resin composition of the present invention can be carried out according to a known method. That is, a resin varnish obtained by dissolving the resin composition in an organic solvent is impregnated into a base material, heat-treated to form a prepreg, and then the prepreg and copper foil are laminated by heating to form a copper-clad laminate. The organic solvents used are toluene, xylene, N, N-dimethylformamide, N, N
-Dimethylacetamide, N-methyl-2-pyrrolidone, methyl ethyl ketone, methyl isobutyl ketone, dioxane, tetrahydrofuran and the like can be selected alone or as a mixture of two or more solvents.

The base material to be impregnated with the resin varnish includes inorganic fibers such as glass fibers, polyester fibers, and polyamide fibers;
Woven or non-woven fabric or mat made of organic fiber,
Paper and the like can be used alone or in combination. The heat treatment conditions for the prepreg are the solvent used,
It is appropriately selected according to the type and amount of the added catalyst and various additives, but is usually performed at a temperature of 80 ° C to 220 ° C for 3 minutes to 30 minutes. Heat molding condition is 150 ℃ ～ 30
0 temperature 10kg / cm ² ~100kg / cm 20 to 300 minutes of heat-pressed at ² of the molding pressure ℃ are exemplified.

[0039]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Synthesis Example 1 (1) Synthesis of o-toluidine oligomer (intermediate polyamino oligomer): 2000 ml of a reflux condenser equipped with a Dean-Stark tube, a thermometer, a stirrer, and a nitrogen introducing device for separating water. In a reactor, m-di (α-hydroxyisopropyl) benzene (271 g, 1.4 mol), o
-Charge 37.5 g (0.35 mol) of toluidine, 308.5 g of xylene and 65.3 g of acid clay, and raise the temperature to 120 ° C. while stirring. Furthermore, the internal temperature was reduced to 210 while removing the distillate with a Dean-Stark tube.
The temperature was raised to 0 ° C. and kept for 7 hours.

At this time, the total amount of distillate was 57.0 g. Then, the mixture was cooled until the internal temperature reached 140 ° C., and 75 g (0.7 mol) of o-toluidine was added.
The temperature was raised to 10 ° C. and kept at that temperature for 12 hours. After the completion of the reaction, the reaction mixture is cooled until the internal temperature becomes 100 ° C. or lower, diluted with 313.1 g of toluene, and the acid clay is removed by filtration. The solvent and unreacted substances and other low molecular weight substances are distilled off under reduced pressure to obtain the o-toluidine oligomer 2 as the target substance.
54.8 g were obtained. The amine equivalent was 393 g / eq and the softening point was 64.8 ° C. The average repetition unit number n value (number average) of the general formula (2) was determined by liquid chromatography to be 2.6.

(2) Synthesis of o-toluidine oligomer polymaleimide: A method for producing a polymaleimide compound used in the present invention by reacting an o-toluidine oligomer with maleic anhydride will be described. Reflux condenser, thermometer,
100 g of the o-toluidine oligomer obtained in Synthesis Example 2 was placed in a 2000 ml reactor equipped with a stirrer and a nitrogen introducing device.
(0.254 mol equivalent, amino group equivalent 393 g / e
q), 29.9 g (0.305 mol) of maleic anhydride
And 303.3 g of acetone were charged and dissolved by stirring at room temperature. After dissolution, the temperature was raised to 40 ° C. and maintained at that temperature for 9 hours. Then, 33.8 g of acetic anhydride (0.331 mol)
l), nickel acetate tetrahydrate 0.28 g (1.1 mol)
l) and 1.92 g of triethylamine (19.0 mol)
1) was added, and the temperature was raised to 60 ° C. and maintained at that temperature for 8 hours. After the completion of the reaction, the mixture was cooled to room temperature, and 303.0 g of toluene was used.
Diluted. After washing with a dilute aqueous sodium hydrogen carbonate solution and then with water and azeotropic dehydration, inorganic salts were removed by filtration. By removing the solvent under reduced pressure, 101.9 g of the desired polymaleimide compound was obtained. Softening point is 110
° C. As a result of infrared absorption spectrum measurement of the product,
Absorption from indane structure (2960, 1490, 146
0, 1430, 765 cm ^-1 ) and absorption (1715, 1805 cm ^-1 ) derived from a maleimide structure.

Synthesis Example 2 (1) Synthesis of 2,6-xylysine oligomer (intermediate polyamino oligomer): equipped with a reflux condenser equipped with a Dean-Stark tube, a thermometer, a stirrer, and a nitrogen introducing device for separating water. 972 g (6.15 mo) of m-di (α-hydroxyisopropyl) benzene was added to the 5000 ml reactor.
l), 303 g of 2,6-xylidine (2.50 mo
1), 1275 g of xylene and 334 g of acid clay are charged, and the temperature is increased to 120 ° C. while stirring.
Further, while removing the distillate with a Dean-Stark tube, the temperature is raised until the internal temperature becomes 210 ° C., and the temperature is kept for 3 hours.

At this time, the total amount of distillate was 214.4 g. Then, cool until the internal temperature reaches 140 ° C.
After charging 1052 g (8.69 mol) of xylidine, the temperature was raised until the internal temperature reached 220 ° C., and maintained at that temperature for 3 hours. After the completion of the reaction, the reaction mixture is cooled until the internal temperature becomes 100 ° C. or lower, diluted with 1500 g of toluene, and the acid clay is removed by filtration. The solvent and unreacted substances and other low molecular weight substances were distilled off under reduced pressure to obtain 1310 g of the objective 2,6-xylysine oligomer. The amine equivalent is 29
2g / eq, and the softening point was 60.6 ° C.

As a result of measuring the infrared absorption spectrum of the product obtained by this method, 2960, 1490, 1461, 144 characteristic of the indane skeleton of the general formula (2) were obtained.
An absorption of 0.755 cm ^-1 was observed. FD-M of product
As a result of the S spectrum measurement, the above general formula (1) (provided that X
Is m / e = 400 with respect to the structure of the general formula (2).
(N '= 0), 558 (n' = 1), 716 (n '=
2), 874 (n '= 3) was detected as the main peak. Here, n ′ represents the number of repeating units of X. The average repetition unit number n value (number average) of the general formula (2) was determined by liquid chromatography using a calibration curve based on the results of mass spectrometry, and was 0.92.

(2) Synthesis of 2,6-xylidine oligomer polymaleimide: A method for producing a polymaleimide compound used in the present invention by reacting a 2,6-xylidine oligomer with maleic anhydride will be described. Reflux condenser,
5000 m with thermometer, stirrer and nitrogen introduction device
308 g of the 2,6-xylidine oligomer obtained in Synthesis Example 1 (1.05 equivalent, amino group equivalent 292 g)
/ Eq), 113.8 g of maleic anhydride (1.16 mo)
l) and 984.2 g of methyl isobutyl ketone were charged and dissolved by stirring at room temperature. After dissolution, the temperature was raised to 40 ° C. and maintained at that temperature for 6 hours. Then, acetic anhydride 151.
8 g (1.05 mol), nickel acetate tetrahydrate 1.1
0 g (3.78 mmol) and triethylamine 7.
94 g (78.6 mmol) was added, the temperature was raised to 60 ° C., and the temperature was maintained for 8 hours. After completion of the reaction, the mixture was cooled to room temperature and diluted with 703 g of methyl isobutyl ketone. After washing with a dilute aqueous sodium hydrogen carbonate solution and then with water and azeotropic dehydration, the inorganic salts were removed by filtration. By removing the solvent under reduced pressure, the objective polymaleimide compound 305.
8 g were obtained. The softening point was 98.1 ° C. As a result of infrared absorption spectrum measurement of the product, the absorption derived from the indane structure (2960, 1485, 1460, 1440, 760c)
m ^-1 ) and the absorption derived from the maleimide structure (1715, 18
05 cm ^-1 ).

Examples 1-2 The polymaleimide compound and triallyl isocyanurate obtained in Synthesis Examples 1 and 2 were dissolved in toluene to obtain a uniform resin varnish. The varnish was impregnated into glass cloth (trade name: KS-1600, E-glass, manufactured by Kanebo Co., Ltd.), and
The prepreg was heat-treated in an 80 ° C. hot air drier for 10 to 20 minutes. Six prepregs and copper foil (Furukawa Electric Co., Ltd.)
(TTAI treated product, 35 μm thick), 200 ° C, 50
Press molding at a pressure of kg / cm ² for 2 hours and then 250
This was cured at 5 ° C. for 5 hours to obtain a copper-clad laminate having a thickness of 1 mm.

The glass transition temperature, copper foil peeling strength, solder heat resistance, boiling water absorption and dielectric constant of the laminate were measured.
The glass transition temperature was measured using a dynamic viscoelasticity measuring device, Rheograph Solid, manufactured by Toyo Seiki Co., Ltd., and the temperature at which the loss modulus was maximized was adopted. The value of the dielectric constant is Multi-Frequency L manufactured by Yokogawa Hewlett-Packard Co., Ltd.
Room temperature, 1M determined by CR meter 4275A
It was calculated from the capacitance of the sample in Hz. Other physical properties of the laminate were measured according to JIS-C-6481. Table 1 shows the measurement results.

Example 3 The polymaleimide compound obtained in Synthesis Example 2 and 4,4′-
Diaminodiphenylmethane (trade name: Sumicure M, manufactured by Sumitomo Chemical Co., Ltd.) was dissolved in toluene, and the obtained resin varnish was formed into a copper-clad laminate in the same manner as in Examples 1 and 2. The physical properties of this laminate were measured in the same manner as in Examples 1 and 2. Table 1 shows the results.

Comparative Example 1 N, N '-(4,4'-diaminodiphenylmethane) bismaleimide (trade name Bestrex BH-180, manufactured by Sumitomo Chemical Co., Ltd.) and 4,4'-diaminodiphenylmethane (trade name) Sumicure M, Sumitomo Chemical Co., Ltd.
Was dissolved in N, N-dimethylformamide, and the obtained resin varnish was prepared in Examples 1 and 2 at 200 ° C.
Except for 3 hours.
The physical properties of this laminate were measured in the same manner as in Examples 1 and 2. Table 1 shows the results.

[0051]

[Table 1]

Examples 4 to 8 The polymaleimide compound obtained in Synthesis Example 2 and various aromatic diamine compounds were blended in the proportions shown in Table 2 and melted by heating to obtain a uniform resin mixture. The resin mixture was molded at 200 ° C. for 2 hours with a press molding machine, and post-cured at 250 ° C. for 5 hours to obtain a cured resin. The glass transition temperature and the dielectric constant of the cured resin were measured. The glass transition temperature was determined by a thermal analyzer DT-30 manufactured by Shimadzu Corporation, and the value of the dielectric constant was determined by Multi manufactured by Yokogawa Hewlett-Packard Co., Ltd.
i-Frequency LCRmeter 4275
Calculated from the capacitance of the sample at room temperature and 1 MHz obtained by A. Table 2 shows the measurement results.

COMPARATIVE EXAMPLE 2 A resin composition having the same composition as in Comparative Example 1 was heated and melt-mixed without using a solvent.
A cured resin was obtained in the same manner except that the curing was performed for a long time. Table 2 shows the results of measuring the glass transition temperature and the dielectric constant in the same manner as in Examples 4 to 8.

[0054]

[Table 2]

[0055]

The thermosetting resin composition of the present invention thus obtained and the copper-clad laminate thereof are excellent in heat resistance and have a low dielectric constant, so that they are useful for multilayer printed circuit boards.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI H05K 1/05 H05K 1/05 // C08F 299/02 C08F 299/02 (72) Inventor Kunimasa Kamio 6 Kitahara, Tsukuba, Ibaraki Prefecture Sumitomo Chemical Co., Ltd. (56) References JP-A-2-24324 (JP, A) JP-A-63-275562 (JP, A) JP-A-62-181335 (JP, A) (58) Fields investigated (Int. Cl ^7, DB name) C08G 73/00 -. 73/26 C08L 79/00 - 79/08

Claims (4)

(57) [Claims] 1. A compound represented by the general formula (1): (Wherein P is independently an alkyl group having 1 to 10 carbon atoms, an alkyloxy group or an alkylthio group, an aryl group having 6 to 10 carbon atoms, an aryloxy group or an arylthio group, a cycloalkyl group having 5 to 10 carbon atoms) , Represents a halogen atom, a nitro group, a hydroxyl group or a mercapto group,
j represents an integer value of 0 or more and 4 or less. When j is 2 or more and 4 or less, P may be the same or different in the same ring. Q independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group or an alkylthio group, an aryl group having 6 to 10 carbon atoms, an aryloxy group or an arylthio group, a halogen atom, a hydroxyl group or a mercapto group; Indicates an integer value of 3 or less. k is 2 or more and 3
In the following cases, Q may be the same or different in the same ring. X is a general formula (2): (Wherein, Q and k are the same as described above, n is the average number of repeating units, and is a numerical value of 0.5 or more and 20 or less). )
A thermosetting resin composition comprising: a polymaleimide compound (A) represented by the formula: and a reaction component (B) that reacts with the polymaleimide compound to form three-dimensional crosslinking. 2. The thermosetting resin composition according to claim 1, wherein said reaction component (B) is triallyl cyanurate. 3. The thermosetting resin composition according to claim 1, wherein said reaction component (B) is an aromatic diamine. 4. A prepreg obtained by dissolving the thermosetting resin composition according to claim 1, 2 or 3 in an organic solvent, impregnating a substrate, and drying, and laminating and heat laminating. Copper clad laminate.